Oxidation behavior and electrical properties of metal interconnects with Ce-doped Ni–Mn spinel coatings

To improve the high-temperature oxidation resistance and electrical conductivity of ferritic stainless steels, protective Ce-doped NiMn₂O₄ spinel coatings were fabricated on the surface of SUS430 steel by electrophoretic deposition (EPD). The phase structure and microstructure of Ce-doped NiMn₂O₄ in both powder and coating forms were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The high-temperature oxidation of the NiMn₂O₄ spinel coating before and after Ce doping in the air at 800 °C for 168 h was studied by weight gain experiments. The area-specific resistance (ASR) of coatings was measured by a standard four-probe method. It was found that the Ce-doped NiMn₂O₄ spinel powder displayed a stable structure, high crystallinity, fine grain size, and decreased agglomeration when the Ce content was fixed at 0.05 mol?L^?1. The oxidation kinetics of NiMn₂O₄-coated SUS430 steel before and after Ce doping obeyed a parabolic law with parabolic rate constants of 4.58 × 10^?15 g² cm^?4 s^?1 and 1.83 × 10^?15 g² cm^?4 s^?1, respectively. When oxidized at 800 °C for 50 h, the ASR value of the coated samples before and after Ce doping stabilized at about 15.2 mΩ?cm² and 14.5 mΩ?cm², respectively. This work demonstrated that the Ce-doped NiMn₂O₄ spinel coating improved the high-temperature oxidation resistance and the electrical conductivity of metal interconnects.     

Thermodynamic calculation and microstructure characterization of spinel formation in MgO–Al2O3–C refractories

In this paper, by simulating the gas phase conditions inside the MgO–Al₂O₃–C refractories during continuous casting process and combining with thermodynamic analysis, as well as SEM analysis, the gas-gas and gas-solid formation of MA spinel were clarified in carbon containing refractories. Thermodynamic calculations showed that gas partial pressure of CO, O₂ and Mg could meet the formation and stable existence conditions of MA spinel in MgO–Al₂O₃–C refractories under service environment, and nitrogen could not affect the formation of MA spinel at 1550 °C in the thermodynamic condition. The formation processes of MA spinel were analyzed experimentally under embedding carbon atmosphere. The carbon-coated alumina powders in MgO–Al₂O₃–C refractories prevented the direct contact between magnesia and alumina. Mg gas was formed by carbon thermal reaction, then reacted with alumina (gas-solid) and gas containing aluminum (gas-gas) to generate MA spinel. Through gas-gas or gas-solid reaction, the formation of MA spinel was effectively controlled. By means of SEM analysis, a two-layer structure with dense outer spinel layer and loose inner layer was formed in MgO–Al₂O₃–C refractories.     

用废弃含碳耐火材料合成方镁石-镁铝尖晶石复相材料

以废弃镁碳砖与废弃滑板为原料,分别按照n(MgO)/n(Al2O3)=1,2,3,4比例进行制样,通过1300℃、1400℃、1500℃保温2h对试样进行煅烧.用X射线衍射仪、扫描电镜及X' Pert plus软件对热处理后试样的组成和结构进行表征.结果发现:以废弃镁碳砖与废弃滑板可以合成出方镁石-尖晶石复相材料,随着废弃镁碳砖引入量增加;试样体积密度降低,显气孔率增加,结构组成中方镁石逐渐增加.煅烧温度的增加促进方镁石与刚玉相形成镁铝尖晶石相.当n(MgO)/n(Al2O3)=3,煅烧温度1500℃时,经煅烧后形成方镁石-尖晶石复相结构中结晶相方镁石含量达到33％,镁铝尖晶石59％,方镁石-尖晶石相间由结晶度较差的玻璃相粘结.     

抗水合氧化铝载体研究进展

氧化铝系载体用于含水或有水生成的催化过程时，均会发生再水合现象，从而造成催化剂强度的下降，并导致其比表面积大幅下降，使催化剂不可逆失活。镁铝尖晶石的抗水合性远高于氧化铝系载体，是一种很好的催化剂载体。综述了氧化铝系载体的再水合现象、改进载体抗水合性能的方法以及镁铝尖晶石粉体和载体的制备方法及改进措施。     

含硅的铁酸镁在苯酚过氧化氢羟化反应的催化作用

以苯酚过氧化氢羟基化制取苯二酚为背景,采用共沉淀法制备了对苯酚过氧化氢羟基化具有高活性的含硅的铁酸镁(MgxFey(SiO4))尖晶石类催化剂,对所制备的含硅的该催化剂的结构进行了分析表征,并研究了它们的苯酚羟化活性。     

ZnO对M9O-Al2O3-SiO2微晶玻璃结构与透光性能的影响

研究了MgO-Al2O3-SiO2系统微晶玻璃中ZnO含量对微晶玻璃结构及透光性能的影响.采用差热分析、X射线衍射、场发射扫描电镜、紫外-可见-近红外分光光度计对材料进行测试.结果表明:透明微晶玻璃主晶相为尖晶石晶体:ZnO含量的增加使玻璃析晶程度提高,析出晶体尺寸变小且分布更加均匀;添加2%(质量分数,下同)的ZnO可使晶粒尺寸显著减小,得到透明微晶玻璃样品平均晶粒尺寸为27nm,在可见光区透过率大于85%:当ZnO含量从0%增加到4%时,透明微晶玻璃的紫外吸收极限逐渐向短波方向移动.

Abstract：

The influence of zinc oxide (ZnO) addition on the microstructure and transparent property of MgO-Al2O3-SiO2 glassceramics was investigated by using differential thermal analysis, X-ray diffraction, field emissionenvironment scanning electron microscope and ultraviolet-visible-near infrared scanning spectrophotometer. The results show that cubic spinel is the main crystalline phase in the transparent glass-ceramics.The crystallinity increased, the crystalline grain size decreased and became more uniform with increasing ZnO content. The average grain size was 27 mn, and the transmittance of the glass-ceramic was more than 85% in visible spectra region at ZnO content of 2% (in mass, the same as below). The ultraviolet cut-off wavelength moved to the shorter wave when ZnO content increased from 0% to 4%.     

The study of lithium ion de-insertion/insertion in LiMn2O4 and determination of kinetic parameters in aqueous Li2SO4 solution using electrochemical impedance spectroscopy

In this work, we report a basic study on the mechanism of lithium ion de-insertion/insertion process from/into LiMn₂O₄ cathode material in aqueous Li₂SO₄ solution using electrochemical impedance spectroscopy (EIS). An equivalent circuit distinguishing the kinetic parameters of lithium ion de-insertion/insertion is used to simulate the experimental impedance data. The fitting results are in good agreement with the experimental results and the parameters of the kinetic process of Li⁺ de-insertion and insertion in LiMn₂O₄ at different potentials during charge and discharge are obtained using the same circuit. The results indicate that the de-insertion/insertion behavior of lithium ions at LiMn₂O₄ cathode in Li₂SO₄ aqueous solution is similar to that reported in the organic electrolytes. The charge transfer resistance (R_ct), warburg resistance, double layer capacitance and chemical diffusion coefficient (DLi+) vary with potentials during de-insertion/insertion processes. R_ct is lowest at the CV peak potentials and the important kinetic parameter, DLi+ exhibits two distinct minima at potentials corresponding to CV peaks during de-insertion–insertion and it was found to be between 10⁻⁸ and 10⁻¹⁰ cm² s⁻¹during lithium de-insertion/insertion processes.     

尖晶石纳米催化剂应用于烯丙醇多相氧化制烯丙醛或烯丙酮

使用共沉淀法通过Ru对MeFe2O4的同晶取供制备了纳米级MnFe1.95Ru0.05O4催化剂。在通过过渡金属进一步改性该催化剂的过程中，发现MnFe1.95Ru0.05O4的催化剂性能优异于文献报道的其他多相醇氧化催化剂，XRD测试表明该催化剂仍保持尖晶石结构。该纳米催化剂能有效地将不同烯丙醇类氧化成烯丙醛类或烯丙酮类，与文献报道的其他多相氧化催化体系相比，该催化剂具有更高的活性转换数。借助于EXAFS等表征结果和1－辛醇与4－辛醇的竞争反应，判断出单核的Ru类反应的活性中心，EXAFS的表征同时表明由于Cu的添加而产生的Ru=0能加快反应速率。作者在此基础上提出反应机理，认为Ru在反应过程中形成醇化物，再经过β消除反应生成相应的醛或酮。     

加入ZnO对含Al低碳MgO-C耐火材料抗氧化性的影响

以质量分数为70%的粒度≤3 mm和24%的粒度<0.074 mm的电熔镁砂,3%的粒度<0.15 mm的鳞片石墨,3%的粒度<0.045 mm的金属铝粉为原料,外加4%的酚醛树脂制备了含Al低碳MgO-C耐火材料。加入1%(w)的<0.045 mm的ZnO替代电熔镁砂粉,研究了加入ZnO对含Al低碳MgO-C材料抗氧化性的影响。通过对比这两种材料的显气孔率、常温耐压强度,试样基质的物相变化来探讨原位尖晶石的生成与基质中加入ZnO之间的关系,并通过对比试样中脱碳层与原始层之间出现的致密MgO层来讨论两种低碳MgO-C材料抗氧化性的差异。研究表明:加入ZnO能够在MgO-C材料基质中形成ZnAl2O4,并加速尖晶石的原位生成,使得材料中能够更快更多地形成致密的MgO层,最终提高低碳MgO-C耐火材料的抗氧化性。     

Effects of Chrome Oxide Concentrate Powder on Properties of Magnesia Composite Materials

The magnesia composite materials were prepared using fused magnesia,used magnesia chrome bricks, magnesium aluminate spinel, alumina powder and chrome oxide powder as starting materials. In order to improve the performance of magnesia composite material,the influence of chrome oxide concentrate powder on the properties of magnesia composite material was researched. The apparent porosity,bulk density,cold crushing strength,linear expansion and thermal shock resistance of the specimens were determined. The results show that adding chrome oxide concentrate promotes the formation of the composite phases of three kinds of spinel,which is beneficial to the thermal shock resistance. The magnesia chrome spinel can not be formed at high temperatures theoretically,but can dissolve in the magnesia composite material. Comprehensively,the optimal addition of chrome oxide concentrate is 10. 0 mass% for the magnesia composite materials.